Experimental and theoretical cooling velocity profile inside laser welded metals using keyhole approximation and Boubaker polynomials expansion

In this paper we are concerned with the t-dependent cooling velocity during laser welding sequences. The temperature profile has been yielded by using keyhole approximation for the melted zone and solving the heat transfer equation. A polynomial expansion has been adopted as a guide to determining the cooling velocity during welding cut-off stage. A thorough comparison with experimental results and recently published profiles has been carried out.     

Spectroscopic Characterization of Thiazole Orange-3 DNA Interaction

The interaction of a new derivative of thiazole orange (TO-3) with calf thymus DNA (ctDNA) has been investigated by fluorescence and absorption spectroscopy. When TO-3 binds to ctDNA, absorption bands exhibit significant hypochromicity at low base pair/dye ratio (BP/D ratio), and high BP/D show hyperchromicity with red shift. The spectral changes are attributed to the different species formed between TO-3 and ctDNA in the titration course of the dye molecule with DNA. Multivariate curve resolutions–alternating least squares (MCR–ALS) is applied to the absorption measurements recorded to recover the concentration profiles and the pure spectra of the DNA/TO-3 complexes involved in the process. The binding constant and size of the binding site have been determined spectrophotometrically using the McGhee von Hippel equation. MCR–ALS has been used to reveal the precise concentration profiles of all detectable species formed between ctDNA and TO-3 and their pure spectral profiles.     

PREDICTION OF OIL SATURATION IN A FIBROUS BED COALESCER FROM PRESSURE DROP DATA

A model has been formulated for the prediction of average saturation and the saturation profile through a fibrous bed during coalescence of secondary dispersion. The approach utilizes the Blake-Kozeny equation to relate experimental pressure drop data to saturation in the bed. Reasonable agreement was obtained between predicted saturations and those measured experimentally. The predicted saturation profiles could be used to determine other coalescer design parameters.     

Efficiency of Cd(II) removal from aqueous media using chemically modified polystyrene foam

The removal of Cd(II) using polystyrene foam chemically modified with 2,2′-bipyridine has been investigated. The modified polystyrene foam has been characterized by FT-IR spectroscopy, thermogravimetry, elemental analysis and scanning electron microscopy. The solid was employed as a Cd(II) adsorption from aqueous solutions at room temperature. The effects of several variables (pH, shaking speed, agitation time, metal concentration and presence of other ions in the medium) have been studied using batch technique. Flame atomic absorption spectrometry was used to determine the Cd(II) ion concentration in the filtrate after the adsorption process. Maximum sorption 90% was achieved at pH 7 after 30 min of shaking time. Sorbed metal ions have been desorbed with 5 ml of 2 M HNO₃ with the detection limit of 16.7 ng ml⁻¹. The Langmuir, Freundlich and D–R isotherm equation were used to describe partitioning behavior of the system at room temperature. Kinetic and thermodynamic behavior of modified polystyrene foam for Cd(II) ion removal was also studied. Br⁻, PO₄³⁻, Pb²⁺, Ni²⁺ and Cr(VI) suppress the sorption to some extent. The possible sorption mechanism of Cd(II) ions onto modified sorbent is also discussed. Method was utilized to remove Cd(II) ions from aqueous media.     

The unified equation for the evaluation of first order reactions in dynamic electrophoresis

The unified equation was validated for first order reactions in dynamic CE with a data set of 31 250 elution profiles. Comparison with the results from conventional iterative computer simulation revealed that the unified equation is superior in terms of success rate and precision. The unified equation was applied to determine the cis-trans isomerization rate constants of the angiotensin converting enzyme inhibitor captopril. The separation of the rotational cis-trans isomeric drug has been performed in an aqueous 66 mM citric acid/Tris buffer at pH 3.0 in a 50 cm polyacrylamide-coated fused-silica capillary. Interconversion profiles featuring pronounced plateau formation and peak broadening were observed. Activation parameters DeltaH not equal and DeltaS not equal were obtained from temperature-dependent measurements between 10 and 25 degrees C in 2.5 K steps. From the activation parameters the isomerization barriers of captopril at 37 degrees C under acidic conditions were calculated to be DeltaG not equal trans-->cis=90.6 kJ/mol and DeltaG not equal cis-->trans=84.6 kJ/mol. By comparison of the kinetic data with the results obtained under basic conditions (pH 9.3) a mechanism of isomerization could be proposed.     

Modern methods for determining the molar mass distribution of polymers. General considerations and application to sedimentation equilibrium

A new procedure for the determination of the molar mass means M_n, M_w and M_z and of the molar mass distribution W(M) = f(M) of polymers is proposed and applied on measurements of the sedimentation equilibrium. The procedure includes the extrapolation of the experimentally determined polydisperse measurable quantity at different concentrations to zero concentration. From these values the molar mass distribution is calculated by nonlinear least squares routines of the integral equation. This method of calculation is, contrary to the inverse transformation of the integral equation, which has been used up to now, well conditioned and stable. The proposed method has been applied to sedimentation equilibrium. In this case the reduced concentration profiles (interference optic, absorption optic) or reduced concentration gradient profiles (schlieren optic) measured at different concentrations must be extrapolated to zero concentration and followed by nonlinear regression of the integral equation U_w(X) = ∫ W(M) U(X,M) dM. Measurements on polystyrenes with different polydispersities and modalities (e.g. bimodal molar mass distributions), and on the polyelectrolytes sodium polystyrene sulfonate and polyethylene imine exhibit resonable results. The result of the investigation is, that the proposed procedure is a suitable and reasonable possibility for the determination of molar mass distribution of polymers by sedimentation equilibrium. For polyelectrolytes in particular this method is better than gel permeation or size exclusion chromatography.     

Reaction kinetics in anionic copolymerization: A revisit on Mayo-Lewis equation

Reactivity ratio is a traditional parameter quantifying the reaction kinetics in copolymerization, which is important for potentially controlling microstructures of polymers and guiding the copolymerization process. Our recent experiments using tube-NMR technique enable us to in situ monitor the concentration profiles of the co-monomers during the anionic copolymerization process. This motivates us to revisit the Mayo-Lewis(ML) equation, which is the basis for derivation of reactivity ratio and has been extensively utilized in addition copolymerization. We found that although an explicit ML expression is desirable for ease of calculation and correlation with experimental data, it fails in our anionic copolymerization experiment as well as some data available in the literature. The origin is ascribed to the validity of the steady state assumption which is essential in the ML equation. This assumption can be released in anionic copolymerization and replaced by the fact that the overall concentration of the living chain ends keeps constant throughout the copolymerization. Alternative numerical method has been utilized to obtain the rate constants and consequently the reactivity ratios. Our work suggests that the ML equation should be applied with caution.     

Potentiometric selectivity coefficients of liquid ion-exchange membranes for univalent and divalent ions

Digital simulation has been used to calculate potential—activity responses and concentration-dependent selectivity coefficients for membranes bathed in mixtures of univalent and divalent ions. For an ideal, dissociated, univalent-site liquid ion-exchange membrane, more accurate computations, based on Nernst—Planck equations, were possible than have been reported previously. Simulation results were used with four suggested equations for the membrane potential (including the IUPAC recommendation) to determine which equation gives best fit and most nearly constant selectivity coefficients. When concentration profiles found by digital simulation are employed, improved response equations are given which closely describe the dependence of surface concentrations on the mobility ratio for the bi-ionic case. From these equations a closed form solution to the diffusion equation yields an explicit expression relating the bi-ionic selectivity coefficient to membrane loading, single ion partition coefficients, and ion mobilities.     

Extended version of the van der Waals capillarity theory

An extended version of the van der Waals capillarity theory describing the liquid-vapor interface in the temperature range from the triple to the critical point is suggested. A model functional of thermodynamic potential for a two-phase Lennard-Jones system taking into account the effect of the highest degree terms of gradient expansion has been constructed. The identity of the thermodynamic and the mechanical definition of Tolman's length has been proved in the framework of the adopted form of functional. The properties of nuclei of the liquid and the vapor phase are described. The paper determines: the work of formation of a nucleus, density profiles, size dependences of the surface tension, and the parameter delta in the Gibbs-Tolman-Koenig-Buff equation.     

Estimation of binding sites from the adsorption profile of complexed DNA

The adsorption profiles of free and Daunomycin bound DNA at an alumina–H₂O interface have been studied. Proper experimental conditions were maintained to considerably reduce intercalation and to make electrostatic binding predominant in the DNA–Daunomycin complex. For both free and complexed DNA, Langmuir plots gave straight lines. Adsorption of drug bound DNA was less than that of free DNA. This has been explained from the viewpoint of electrostatic interactions between adsorbate and adsorbent. A Langmuir-type model for adsorption of polymers combined with Scatchard equation have been used to estimate the average value of percent of phosphates in DNA stacked with Daunomycin.     

Four-Level Decay Model of~6P_(7/2) Excited State of Eu~(2+) Ion in KMgF_3

Optical transitions of divalent Europium (4f7) ions in KMgF3 have been investigated extensively due to the potential applications for phosphors or lasers. In KMgF3: Eu2+, the 6P7/2 state is at lower energy than the lowest 4f65d state. However, the reported energy differences between the two states vary from author to author. Sardar et al.1 estimated the value of 1250 cm-1 from a semilog plot of the 6P7/2?8S7/2 and 4f65d? 8S7/2 emission intensities versus T-1. Altshuler et al.2 found the …     

Effects of type of adsorption isotherms on parallel diffusion of sulfonated dyes into porous cellulose membrane

Transport phenomenon of three sulfonated azo dyes, C.I. Acid Red 88, C.I. Direct Yellow 12, and C.I. Direct Blue 15 into water-swollen cellulose membranes has been analyzed on the basis of parallel transport theory by surface and pore diffusion. Langmuir equation was applied into the mass balance equation to estimate dye concentration in the pores. The results were compared with the results obtained by applying Freundlich equation in our previous papers. The surface diffusivity (D _s) and the pore diffusivity (D _p) for the parallel diffusion model obtained by applying Langmuir equation agreed with those obtained by applying Freudlich equation. The theoretical concentration profiles for parallel diffusion calculated usingD _s andD _p coincided accurately with the experimental data when we applied either Langmuir or Freundlich equations.     

Dynamic Adsorption of Vapours by Activated Carbons and by Polymer-Derived Adsorbents: 1. Adsorption at 0% R.H.

The uptakes of volatile organic compounds from a nitrogen carrier gas at 0% R.H. onto packed beds of adsorbents have been measured by monitoring the effluent vapour concentration profile as a function of time. The profiles have been quantitatively fitted by a modified Bohart-Adams equation which was then integrated to yield the adsorbent capacities. Traditional activated carbons, carbonised macroreticular resins and a macroreticular polymer were used in the study. Performance in the dynamic tests has been related to the pore volume characteristics and surface areas determined from nitrogen adsorption isotherms. Whilst the extent of micropore filling basically increased as the sorbate boiling point increased and increased capacities reflected increased micropore volumes, these trends were interrupted by size exclusion and specific polar interaction effects.     

由L-J流体的FMSA状态方程计算流体的PVT性质

运用Tang等提出的Lennard-Jones (L-J)流体两参数的一阶平均球形近似(FMSA)状态方程, 计算了流体的汽液共存相图和饱和蒸汽压曲线, 以及非饱和区的PVT性质, 并与文献数据进行比较. L-J参数由Tr＜0.95的汽液相共存数据回归得到. 计算结果表明, 对于分子较接近球形的流体, 除临界点附近外, 该方程可以在较大的温度和压力范围内计算真实流体的PVT性质, 结果满意. 对于球形分子, 该方程的精确度随分子尺寸的变大基本保持稳定. 该方程不适用于强极性物质. 在高密度区, 该方程的计算结果明显优于P-R方程. 对于分子偏离球形较远的流体, 该方程的适用性变差, 此时要考虑分子形状的影响, 可采用三参数的FMSA状态方程进行计算.     

Structure of inhomogeneous polymer solutions: a density functional approach

The structure of polymer solutions confined between surfaces is studied using a density functional theory where the polymer molecules have been modeled as a pearl necklace of freely jointed hard spheres and the solvent as hard spheres. The present theory uses the concept of universality of the free energy density functional to obtain the first-order direct correlation function of the nonuniform system from that of the corresponding uniform system, calculated through the Verlet-modified type bridge function. The uniform bulk fluid direct correlation function required as input has been calculated from the reference interaction site model integral equation theory using the Percus-Yevick closure relation. The calculated results on the density profiles of the polymer as well as the solvent are shown to compare well with computer simulation results.     

Graphene foam–based electrochemical capacitors

Electrochemical capacitors (ECs) are a promising technology for energy storage, and future development of sustainable electrode materials is critical to developing these devices. The recent progress and earnest motivation to develop high specific energy capacitors commercially for the emerging market and electronics industry, coupled with the significance and popularity of graphene foam (GF)–based electrode materials in the preparation of functional capacitors have been crucially explored in this review. The review outlines the current disposition and headways in GF-based ECs' technology. Besides, owing to its three-dimensional interconnected hierarchical form alongside the physicochemical distinctions, GF has been regarded as one to curtail some bottlenecks regarding graphene dispersion/restacking in nanocomposite materials. Some of the various techniques to synthesizing high-grade GF that can enable higher energy density of ECs, as well as some key material's features of GF that enhance various performances of the material's composite have also been reviewed.     

A shock tube study of the reactions of CH with CO2 and O2

The formation and consumption of CH radicals during shock-induced pyrolysis of a few ppm ethane diluted in argon was measured by a ring-dye laser spectrometer. Absorption-over-time profiles, measured at a resonance line in the Q-branch of the A²Δ − X²Π band of CH at λ = 431.1311 nm, were recorded and transformed into CH concentrations by known absorption coefficients. By adding some hundred ppm of CO₂ or O₂ to the initial mixtures, the CH concentration profiles were significantly perturbed. Both the perturbed and unperturbed CH concentration profiles have been compared with calculations based on a reaction kinetic model. A sensitivity analysis revealed that the perturbation process was dominated by direct reactions of CH with the added molecules. By fitting calculated to observed CH profiles the following rate coefficients were obtained The experiments were performed in the temperature range between 2500 K and 3500 K. © 1996 John Wiley & Sons, Inc.     

Molecular dynamics simulation of solvent-polymer interdiffusion: Fickian diffusion

The interdiffusion of a solvent into a polymer melt has been studied using large scale molecular dynamics and Monte Carlo simulation techniques. The solvent concentration profile and weight gain by the polymer have been measured as a function of time. The weight gain is found to scale as t(1/2), which is expected for Fickian diffusion. The concentration profiles are fit very well assuming Fick's second law with a constant diffusivity. The diffusivity found from fitting Fick's second law is found to be independent of time and equal to the self-diffusion constant in the dilute solvent limit. We separately calculated the diffusivity as a function of concentration using the Darken equation and found that the diffusivity is essentially constant for the concentration range relevant for interdiffusion.